EP1807549A1 - Method for coating substrates containing antimony compounds with tin and tin alloys - Google Patents

Method for coating substrates containing antimony compounds with tin and tin alloys

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Publication number
EP1807549A1
EP1807549A1 EP05782911A EP05782911A EP1807549A1 EP 1807549 A1 EP1807549 A1 EP 1807549A1 EP 05782911 A EP05782911 A EP 05782911A EP 05782911 A EP05782911 A EP 05782911A EP 1807549 A1 EP1807549 A1 EP 1807549A1
Authority
EP
European Patent Office
Prior art keywords
tin
solution
antimony
metallization
pretreatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05782911A
Other languages
German (de)
French (fr)
Other versions
EP1807549B1 (en
Inventor
Christian Lowinski
Hans-Jürgen SCHREIER
Gerhard Steinberger
Jana Nauman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to EP05782911A priority Critical patent/EP1807549B1/en
Publication of EP1807549A1 publication Critical patent/EP1807549A1/en
Application granted granted Critical
Publication of EP1807549B1 publication Critical patent/EP1807549B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0392—Pretreatment of metal, e.g. before finish plating, etching

Definitions

  • the present invention relates to a method for the currentless deposition of tin and tin alloy layers on substrates containing antimony compounds such as an ⁇ timony trioxide.
  • the method is particularly suitable for producing joinable tin and tin alloy final layers on printed circuit boards containing antimony compounds, the tin and tin alloy final layers being applied onto copper portions of the con ⁇ ductor pattern, which are not covered by the solder stop mask.
  • the term "joinability" means the bondability or solderability of surfaces.
  • antimony compounds serve as flameproofing agents and to im ⁇ prove the stampability for producing through-holes.
  • the term "currentless deposition method” refers to those methods, wherein no external power source is used as it is used in galvanisation methods.
  • a re ⁇ duction bath the electrons required for depositing a metal are provided by the electrolyte.
  • the baths comprise reducing agents such as sodium hypo- phosphite, formaldehyde or boranes being capable of reducing metal ions to the corresponding metals.
  • No reducing agents are required in case of exchange baths because the dissolved metal ions are capable of directly reacting with the respective surface due to the potential difference.
  • Typical examples for this case are gold on nickel and tin or silver on copper.
  • alloys such as tin-silver, tin-bismuth, tin-lead, tin-zinc, tin-nickel, can be applied according to said method.
  • Tin coatings are applied on copper surfaces or on surfaces of alloys on a cop ⁇ per basis by a certain kind of currentless plating by displacement, i.e., immer ⁇ sion plating techniques, such as those disclosed in US 2,891 ,871 , US 3,303,029 and US 4,715,894.
  • immer ⁇ sion plating techniques such as those disclosed in US 2,891 ,871 , US 3,303,029 and US 4,715,894.
  • tin immersion plating tech ⁇ niques a bath is produced which contains an aqueous solution of a tin(ll) salt, and acid, and thiourea or a thiourea derivative as substantial components.
  • an article having a copper surface such as a copper plated circuit board, is immersed into a plating bath for a time period, during which the metallic copper at the surface is oxidized to copper(l) and complexed by thiourea and is displaced at the surface by metallic tin which is obtained by the simultaneous reduction of tin(ll) ions.
  • the article is removed from the bath and rinsed to remove the remaining plating solution.
  • PCBs printed circuit boards
  • Printed circuit boards comprise a non-conducting or dielectric board such as a glass fibre/epoxy board which is plated with a conductive metal layer such as copper on one surface or on both surfaces.
  • the metal layer on the PCB is typically a continuous copper layer which may be in ⁇ terrupted by a pattern of plated through-holes or connection contacts connect ⁇ ing both surfaces of the board.
  • selected portions of the copper layer are removed to form an elevated copper wiring picture pattern of the PCB.
  • Multilayer PCBs are typically assembled by nesting mapped conduct ⁇ ing layers such as a copper-containing layer, with dielectric adhesive layers such as a partially cured B-stage resin, i.e., a prepreg, to form a multilayer sandwich which is, subsequently, linked by heat and pressure.
  • dielectric adhesive layers such as a partially cured B-stage resin, i.e., a prepreg.
  • the manufacture of these types of printed circuit boards is described in "Printed Circuits Hand ⁇ book”, 3rd edition, edited by C. F. Coombs, Jr., McGraw Hill, 1988. Since a conductive layer having a smooth copper surface is not well-suited for being bonded to the prepreg, different treatments of the copper surface for increasing the bonding strength between the layers of the multilayer PCB sandwich have been developed.
  • Such a treatment of the copper surface is the use of immersion tin and tin alloy compositions as a bonding medium for multilayer circuits as disclosed by Holtzman et al. in US 4,175,894.
  • the method discloses an immersion tin com ⁇ position containing both thiourea compounds and urea compounds for plating the copper surface of each PCB by means of the immersion method by replac ⁇ ing tin before being laminated to form a multilayer printed circuit board.
  • US 5,435,838 describes a method for the currentless deposition of a tin bismuth alloy on copper surfaces.
  • tin and bismuth are employed in the form of their methane sulfonates.
  • Thiourea is used as a complexing agent for forming a complex with the copper dissolved from the surface.
  • this class of substrates containing antimony compounds there are, for example, printed circuit boards which use so-called CEM-1 as a cost-effective base material.
  • CEM-1 a cost-effective base material.
  • This material has the advantage that drilling holes which is one of the most complex and most expensive steps in the manufacture of printed circuit boards can be replaced by a simple stamping process.
  • antimony compounds in particular, antimony trioxide as a flameproofing agent and for improving the stampability of the base material. Therefore, exemplarily the company lsola USA describes the content of antimony trioxide in its base material 65M62 to be 5.74%.
  • the antimony trioxide is dissolved out of the base material at the edges and at the stamped holes.
  • a turbidity and dark precipitations in the baths for depositing tin and tin alloys occur.
  • the deposited tin layers exhibit dark stains. Thus, their properties as joinable final layers are not sufficient.
  • the baths for depositing tin and tin alloys cannot be used for the production of metallized substrates already after coating few printed circuit boards. Thus, a commercially reasonable application of coating tin onto CEM-1 printed circuit boards is not possible.
  • WO 94/26082 relates to a method for through-connecting printed circuit boards by means of conductive plastics for direct metallization, wherein a polymer layer having an intrinsic electric conductivity is applied fixedly onto non-conductive positions of the printed circuit boards. A metal layer is applied thereon.
  • the method does not use an oxidative pretreatment of the printed circuit boards.
  • CEM is indicated as a substrate material.
  • the substrate material can be pretreated by certain method measures comprising mechanical clean ⁇ ing, rinsing and etching (cf. page 8, lines 1-4 of WO 94/26082).
  • WO 94/26082 states, inter alia, tin as metal suitable for metallization (cf. page 10, lines 31 - page 11 , line 3).
  • EP 0 926 264 A2 describes an aqueous, strongly acidic exchange bath for cur- rentlessly depositing tin onto copper comprising tin(ll) salts, thiourea or its de ⁇ rivatives, thiohydantoin, a fine grain additive for tin, an emulsifier and a surfac ⁇ tant.
  • Applicant's WO 99/13696 relates to a method for metallizing a substrate having non-conductive surface portions wherein the substrate is treated with a noble metal colloid solution and, subsequently, with an etching solution containing hydrogen ions in a concentration of not more than 0.5 mol/kg solution and hy ⁇ drogen peroxide. Then a first metal layer is produced on the non-conductive surfaces by currentless metal deposition and a second metal layer is applied thereon by electrolytic metal deposition.
  • the method includes the use of hydrogen peroxide as an oxidizing agent.
  • the pretreatment solution used according to the present invention does not contain any oxidizing agents such as the peroxides commonly used in etch ⁇ ing processes (mostly in combination with sulfuric acid) such as hydrogen per ⁇ oxide, peroxodisulfates or persulfates.
  • oxidizing agents such as the peroxides commonly used in etch ⁇ ing processes (mostly in combination with sulfuric acid) such as hydrogen per ⁇ oxide, peroxodisulfates or persulfates.
  • the pretreatment solu- tion used according to the present invention contains a strong acid solution as an essential component which may contain impurities entrained from the pro ⁇ duction method of the acid solution. Acids having a technical purity grade can thus be used in the pretreatment solution used according to the present inven ⁇ tion.
  • the interfering effect of the antimony compounds contained in the substrate can be reduced to such an extent that the undesired precipitation is avoided.
  • the tin layers deposited exhibit an excel ⁇ lent quality with respect to the joinability and the durability and the useful life of the tin bath can be extended such that an economic application becomes pos ⁇ sible.
  • the subject of the present invention is a method for the currentless metallization of substrate materials containing antimony compounds with tin or tin alloys, comprising the etching, the metallization with a tin salt solution and rinsing the substrate material, characterized in that the method further comprises a pre ⁇ treatment step wherein the substrate material is contacted with a pretreatment solution prior to the metallization, the pretreatment solution comprising a solu ⁇ tion of a strong acid, being free of oxidizing agents and removing the antimony compounds from the surface of the substrate material prior to the metallization.
  • Strong acids such mineral acids (sulfuric acid, nitric acid, hydrochloric acid) or strong organic acids such as alkane sulfonic acids can be used as pretreatment solutions.
  • strong acids refers to such acids having an acidity constant Ks of 55.34 to 3.16 • 10 "5 corresponding to a pKs of -1.74 to 4.5. Acids having a pKs in the indicated range are used according to the present invention.
  • the concentration of the sulfuric acid in the pretreatment solution used accord ⁇ ing to the present invention is 5-60% (parts by weight of the acid / parts by weight of the solution), preferably 10-30%; the concentration of nitric acid is 5-40%, preferably, 5-25%.
  • methane sulfonic acid in a concentra ⁇ tion of 5-70%, preferably 10-40% can be used as an alkane sulfonic acid.
  • the salts of the acid such as the sodium salt or the potassium salt of methane sulfo ⁇ nic acid can also be used instead of the acids.
  • the term "acid solution” designates an aqueous solution of the acid or its salts. Therefore, also a sodium methanesulfonate solution or a potassium methanesulfonate solution is an acid solution for use in the method according to the present invention.
  • the substrates to be coated are treated with a hydrochloric acid pre ⁇ treatment solution.
  • the content of hydrochloric acid is 5-38%, preferably 10- 30%, particularly preferred 15-25% HCI.
  • the method according to the present invention is usually carried out at a tem ⁇ perature within the range of 15-8O 0 C, preferably 30-70 0 C, and most preferably 50-65 0 C.
  • the treatment period is generally within the range of 1-60 minutes, preferably 1-25 minutes, and particularly pre- ferred 2-10 minutes.
  • the antimony compounds dis ⁇ solved in the pretreatment solution can deposit on the copper surface of the printed circuit boards in the form of antimony. These deposited metal layers can optionally be removed again by a microetching solution.
  • microetching solutions as those usually used to clean copper prior to be ⁇ ing coated with tin or other final layers are known in the art and practically often consist of an aqueous solution of alkali metal peroxodisulfates or hydrogen per ⁇ oxide in combination with sulfuric acid.
  • An etching solution for the surface treatment of copper is described in US 6,036,758, the etching solution contain- ing hydrogen peroxide and an aromatic sulfonic acid or its salt. Additionally, this etching solution contains inter alia an inorganic acid, particularly preferred sulfu ⁇ ric acid.
  • An etching (polishing) solution is known from EP 1 167482, which con ⁇ tains an N-heterocyclic compound, hydrogen peroxide and a salt of dodecyl benzene sulfonic acid.
  • microetching solutions can further be solutions containing sulfuric acid and peroxodisulfate or its salts or caroates.
  • the printed circuit board pretreated according to the method of the present in ⁇ vention can subsequently be metallized chemically in a tin bath. Thereby, the strong dark turbidity of the bath which can otherwise be observed and the for- mation of stains do not occur.
  • the tin final layer exhibits the desired properties such as an excellent joinability and durability.
  • the pretreatment solution according to the present invention has to be replaced continuously because the concentration of anti- mony dissolved therein increases and, consequently, the antimony deposits on the tin copper layers to be coated with tin. This negatively affects the surface properties of the consecutive tin final layer with respect to durability and joinabil ⁇ ity.
  • the antimony can be removed again from the copper by extended etching periods in the microetching step.
  • the time required for the etching step becomes too long, affecting the cost-effectiveness of the method.
  • the pretreatment solution containing antimony compounds is continuously or discontinuously passed over a column containing a metal on which the dissolved antimony species deposits from the pretreatment solution in the form of antimony.
  • the metal can also be added directly to the pretreatment solution. Examples for such metals comprise copper, iron, nickel, cobalt, tin and zinc.
  • the metal can be in the form of granules, rods, bars or spheres, on the surface of which the dissolved antimony deposits.
  • the column When the capacity of the column is exhausted due to the surface being com ⁇ pletely covered with antimony, the column can be regenerated after thorough rinsing by introducing a microetching solution as already described above. After that the column is again available for regenerating the pretreatment solution.
  • the service life of the pretreatment solution can be extended significantly by this measure.
  • the tin bath is continuously or discontinuously passed over metallic tin or metallic tin is directly added to the tin bath.
  • antimony contained in the tin bath deposits on the metallic tin and is thus removed from the bath cycle.
  • regeneration methods known in the art can be used.
  • the regeneration unit disclosed in DE 101 32 478 is used to achieve a constant concentration of tin ions in the solution.
  • the measures described enable an effective chemical metallization of substrate materials containing antimony such as CEM-1 with tin.
  • the service life of baths for depositing tin and tin alloys is strongly increased and the quality of the re ⁇ sulting layers is positively influenced with respect to durability and joinability.
  • the pretreatment solution used in the method according to the present inven ⁇ tion can be regenerated in a further process step. Thereby, the waste water problem is solved to a large extent and the method additionally gains profitabil- ity.
  • Antimony residues which are still leached out of the substrate material in the tin bath and become dissolved, are removed by the regeneration of the tin bath described above by means of metallic tin.
  • a printed circuit board made of CEM-1 material having dimensions of 5 x 5 cm is treated with an aqueous solution containing 18% hydrochloric acid at a tem ⁇ perature of 50 0 C for five minutes. Then the material is treated with a microetch- ing solution ,,Micro Etch SF", available from Atotech, which essentially contains a sulfuric acid solution of peroxodisulfate, at a temperature of 35°C for one min ⁇ ute and is subsequently metallized with tin by employing Atotech's method for the chemical deposition of tin, comprising the following two steps:
  • the tin layer deposited exhibits a thickness of about 0.5 ⁇ m, an excellent dura ⁇ bility and excellent joining properties in terms of solderability.
  • the procedure described is repeated for a total of five times. Thereby, the baths for chemical metallization of the printed circuit boards maintain their initial prop ⁇ erties. The described turbidity and the dark precipitations in the tin bath do not occur. The tin layers deposited do not exhibit any dark stains and their surface properties are maintained.
  • a printed circuit board made of CEM-1 material having dimensions of 5 x 5 cm is treated with an aqueous solution containing 10% hydrochloric acid at a tem ⁇ perature of 60 0 C for five minutes. Then the material is treated with a microetch- ing solution ,,Micro Etch SF", available from Atotech, at a temperature of 35°C for one minute and is subsequently metallized with tin by using Atotech's method for the chemical deposition of tin, comprising the following two steps:
  • the printed circuit boards are rinsed with VE-water and dried at a temperature of 60 0 C.
  • the tin layer deposited exhibits a thickness of about 0.5 ⁇ m, an excellent dura ⁇ bility and excellent joining properties in terms of solderability.
  • the procedure described is repeated for a total of five times. Thereby, the baths for chemical metallization of the printed circuit boards maintain their initial prop- erties. The described turbidity and the dark precipitations in the tin bath do not occur. The tin layers deposited do not exhibit any dark stains and their surface properties are maintained.
  • the aqueous solution containing 18 % hydrochloric acid for the pretreatment of the printed circuit boards is used in accordance with Example 1.
  • a portion of the solution is continuously removed from the bath and passed over a column filled with copper granules.
  • antimony deposits at the surface of the gran ⁇ ules.
  • the copper surface is covered with metallic antimony to a large ex ⁇ tent, the antimony is dissolved by treating with Atotech's microetching solution ,,Micro Etch SF", the solution is removed from the column and supplied to the waste water treatment.
  • Atotech's microetching solution Atotech's microetching solution ,,Micro Etch SF
  • the pretreated printed circuit boards are processed in accordance with Exam- pie 1 or 2.
  • a portion of the Stannatech F-solution for metallizing the substrate with tin ac ⁇ cording to Example 1 is continuously removed from the bath and passed over a column filled with tin granules.
  • antimony deposits on the surface of the granules.
  • the antimony is dissolved by treating with Atotech's microetching solution ,,Micro Etch SF", the solution is removed from the column and supplied to the waste water treatment.
  • the Stannatech F-solution for metallizing the substrate with tin in accordance with Example 1 is added with 50 g tin granules.
  • antimony deposits on the surface of the granules.
  • the tin surface is covered with metallic anti- mony to a large extent, the tin granules are removed from the metallizing solu ⁇ tion and the antimony is dissolved by treating the covered granules with Atotech's microetching solution ,,Micro Etch SF", the solution is supplied to the waste water treatment and the tin granules set free from antimony are supplied back into the metallization solution.
  • a printed circuit board made of CEM-1 material having dimensions of 5 x 5 cm is treated with Atotech's cleaning agent Pro Select SF which is employed as a standard agent in the conventional metallization of printed circuit boards, at a temperature of 40 0 C for five minutes. Then the material is treated with Atotech's microetching solution ,,Micro Etch SF" at a temperature of 35°C for one minute and is subsequently metallized with tin.
  • Atotech's method for the chemical deposition of tin is employed, the method comprising the following two steps:
  • the tin layer deposited initially exhibits an at least sufficient joinability at a thick ⁇ ness of about 0.5 ⁇ m.
  • the Stannatech bath loses its initial properties already in the next metallization step. A turbidity and the formation of dark precipitations occur in the tin bath. The tin layer deposited exhibits dark stains and loses its desired surface proper ⁇ ties. The properties of the tin bath deteriorate rapidly in the following. Already after the fourth step the metallization is incomplete and the bath cannot be used any more.
  • a printed circuit board made of CEM-1 material having the size of 5 x 5 cm is treated without pretreatment with Atotech's microetching solution ,,Micro Etch SF" at a temperature of 35°C for one minute and is subsequently metallized with tin.
  • Atotech's method for the chemical deposition of tin is employed, the method comprising the following two steps:
  • the printed circuit boards are rinsed with VE-water and dried at a temperature of 60 0 C.
  • the tin layer deposited initially exhibits an at least sufficient joinability at a thick ⁇ ness of about 0.5 ⁇ m.
  • the Stannatech bath loses its initial properties. A turbidity and the formation of dark precipitations occur in the tin bath. The tin layer deposited exhibits dark stains and loses its desired surface properties. The properties of the tin bath deteriorate rapidly in the following. Al- ready after few method steps the metallization is incomplete. The bath has to be discarded.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The present invention relates to a method for depositing tin or tin alloy layers on substrates containing antimony compounds as flameproofing agents or for improving the stampability, wherein the antimony compound is removed from the surface of the substrate material by an acid solution prior to metallization. Particularly preferred, pretreatment solutions containing hydrochloric acids are used for this purpose. The method is particularly suitable for producing joinable tin final layers on printed circuit boards containing antimony compounds, the tin final layers being applied onto copper portions of the conductor pattern which are not covered by the solder stop mask.

Description

Method for coating substrates containing antimony compounds with tin and tin alloys
DESCRIPTION OF THE INVENTION
The present invention relates to a method for the currentless deposition of tin and tin alloy layers on substrates containing antimony compounds such as an¬ timony trioxide. The method is particularly suitable for producing joinable tin and tin alloy final layers on printed circuit boards containing antimony compounds, the tin and tin alloy final layers being applied onto copper portions of the con¬ ductor pattern, which are not covered by the solder stop mask. As used herein, the term "joinability" means the bondability or solderability of surfaces.
In this context antimony compounds serve as flameproofing agents and to im¬ prove the stampability for producing through-holes.
During the production of printed circuit boards final layers for producing the joinability are applied onto copper portions of the conductor pattern which are not covered by the solder stop mask, in one of the last production steps. The portions of the printed circuit boards, which are not covered by the copper layer, are particularly those portions of the surface which are not structured by con¬ ductor lines. In these portions the base material comes into direct contact with the solution used for the terminal metallization, e.g., using tin.
For this purpose, currentlessly deposited tin and tin alloy layers gain a still in¬ creasing market share. This is attributed both to the insensitive, reliable method having a wide processing range and to the excellent solderability of tin and tin alloys even after multiple high temperature exposures. Therefore, this layer is superior compared to simple organic protective layers. Furthermore, the method is more cost-effective compared to, for example, applying a nickel gold layer.
The term "currentless deposition method" refers to those methods, wherein no external power source is used as it is used in galvanisation methods. In a re¬ duction bath the electrons required for depositing a metal are provided by the electrolyte. The baths comprise reducing agents such as sodium hypo- phosphite, formaldehyde or boranes being capable of reducing metal ions to the corresponding metals. No reducing agents are required in case of exchange baths because the dissolved metal ions are capable of directly reacting with the respective surface due to the potential difference. Typical examples for this case are gold on nickel and tin or silver on copper.
In the following, currentless methods are described in more detail.
There are various per se known methods available for applying the joinable tin and tin alloy final layer, which are described in the state of the art.
In addition to pure tin layers also alloys such as tin-silver, tin-bismuth, tin-lead, tin-zinc, tin-nickel, can be applied according to said method.
Already for a long time tin final layers are applied according to currentless methods to coat the surfaces of work pieces with copper or copper alloys with the purpose of forming corrosion resistant surfaces. In these currentless meth¬ ods the base metal is dissolved as a compensation for the tin ions deposited.
Tin coatings are applied on copper surfaces or on surfaces of alloys on a cop¬ per basis by a certain kind of currentless plating by displacement, i.e., immer¬ sion plating techniques, such as those disclosed in US 2,891 ,871 , US 3,303,029 and US 4,715,894. In these disclosed tin immersion plating tech¬ niques a bath is produced which contains an aqueous solution of a tin(ll) salt, and acid, and thiourea or a thiourea derivative as substantial components. In said tin immersion plating method an article having a copper surface such as a copper plated circuit board, is immersed into a plating bath for a time period, during which the metallic copper at the surface is oxidized to copper(l) and complexed by thiourea and is displaced at the surface by metallic tin which is obtained by the simultaneous reduction of tin(ll) ions. After the desired thick- ness has been achieved by displacement plating, the article is removed from the bath and rinsed to remove the remaining plating solution.
Currentless displacement plating is used in the manufacture of printed circuit boards (PCBs) and, particularly, in the manufacture of multilayer printed circuit boards. Printed circuit boards comprise a non-conducting or dielectric board such as a glass fibre/epoxy board which is plated with a conductive metal layer such as copper on one surface or on both surfaces. Prior to the processing, the metal layer on the PCB is typically a continuous copper layer which may be in¬ terrupted by a pattern of plated through-holes or connection contacts connect¬ ing both surfaces of the board. During the processing selected portions of the copper layer are removed to form an elevated copper wiring picture pattern of the PCB. Multilayer PCBs are typically assembled by nesting mapped conduct¬ ing layers such as a copper-containing layer, with dielectric adhesive layers such as a partially cured B-stage resin, i.e., a prepreg, to form a multilayer sandwich which is, subsequently, linked by heat and pressure. The manufacture of these types of printed circuit boards is described in "Printed Circuits Hand¬ book", 3rd edition, edited by C. F. Coombs, Jr., McGraw Hill, 1988. Since a conductive layer having a smooth copper surface is not well-suited for being bonded to the prepreg, different treatments of the copper surface for increasing the bonding strength between the layers of the multilayer PCB sandwich have been developed.
Such a treatment of the copper surface is the use of immersion tin and tin alloy compositions as a bonding medium for multilayer circuits as disclosed by Holtzman et al. in US 4,175,894. The method discloses an immersion tin com¬ position containing both thiourea compounds and urea compounds for plating the copper surface of each PCB by means of the immersion method by replac¬ ing tin before being laminated to form a multilayer printed circuit board.
US 5,435,838 describes a method for the currentless deposition of a tin bismuth alloy on copper surfaces. In this method tin and bismuth are employed in the form of their methane sulfonates. Thiourea is used as a complexing agent for forming a complex with the copper dissolved from the surface.
However, the described methods for depositing tin and tin alloys are not suit¬ able for coating substrates containing antimony compounds. Antimony com¬ pounds are widespread in industry and are used as flameproofing agents and for improving the stampability such as in the production of printed circuit boards.
This restriction significantly limits the scope of application of chemical methods for applying tin. It is, therefore, the object underlying the present invention to provide a method which can be successfully applied also for the described class of substrates.
Among this class of substrates containing antimony compounds there are, for example, printed circuit boards which use so-called CEM-1 as a cost-effective base material. This material has the advantage that drilling holes which is one of the most complex and most expensive steps in the manufacture of printed circuit boards can be replaced by a simple stamping process. Until now it has not been possible to coat CEM-1 materials according to a currentless tin method. The reason is the use of antimony compounds, in particular, antimony trioxide as a flameproofing agent and for improving the stampability of the base material. Therefore, exemplarily the company lsola USA describes the content of antimony trioxide in its base material 65M62 to be 5.74%. During the process steps the antimony trioxide is dissolved out of the base material at the edges and at the stamped holes. As a result, a turbidity and dark precipitations in the baths for depositing tin and tin alloys occur. The deposited tin layers exhibit dark stains. Thus, their properties as joinable final layers are not sufficient. Furthermore, the baths for depositing tin and tin alloys cannot be used for the production of metallized substrates already after coating few printed circuit boards. Thus, a commercially reasonable application of coating tin onto CEM-1 printed circuit boards is not possible.
WO 94/26082 relates to a method for through-connecting printed circuit boards by means of conductive plastics for direct metallization, wherein a polymer layer having an intrinsic electric conductivity is applied fixedly onto non-conductive positions of the printed circuit boards. A metal layer is applied thereon. The method does not use an oxidative pretreatment of the printed circuit boards. Among others, CEM is indicated as a substrate material. The substrate material can be pretreated by certain method measures comprising mechanical clean¬ ing, rinsing and etching (cf. page 8, lines 1-4 of WO 94/26082).
Finally, WO 94/26082 states, inter alia, tin as metal suitable for metallization (cf. page 10, lines 31 - page 11 , line 3).
EP 0 926 264 A2 describes an aqueous, strongly acidic exchange bath for cur- rentlessly depositing tin onto copper comprising tin(ll) salts, thiourea or its de¬ rivatives, thiohydantoin, a fine grain additive for tin, an emulsifier and a surfac¬ tant.
Applicant's WO 99/13696 relates to a method for metallizing a substrate having non-conductive surface portions wherein the substrate is treated with a noble metal colloid solution and, subsequently, with an etching solution containing hydrogen ions in a concentration of not more than 0.5 mol/kg solution and hy¬ drogen peroxide. Then a first metal layer is produced on the non-conductive surfaces by currentless metal deposition and a second metal layer is applied thereon by electrolytic metal deposition.
The method includes the use of hydrogen peroxide as an oxidizing agent. Surprisingly, the problems described can be solved by a simple pretreatment of the substrate materials containing antimony with a pretreatment solution by which the antimony compounds can be removed from the surface.
Therein, the pretreatment solution used according to the present invention does not contain any oxidizing agents such as the peroxides commonly used in etch¬ ing processes (mostly in combination with sulfuric acid) such as hydrogen per¬ oxide, peroxodisulfates or persulfates. The use of such oxidizing agents results in the metals being peeled off from a metallic substrate such as copper of a printed circuit board. Thus, the surfaces are roughened. The pretreatment solu- tion used according to the present invention contains a strong acid solution as an essential component which may contain impurities entrained from the pro¬ duction method of the acid solution. Acids having a technical purity grade can thus be used in the pretreatment solution used according to the present inven¬ tion.
By applying the method according to the present invention, the interfering effect of the antimony compounds contained in the substrate can be reduced to such an extent that the undesired precipitation is avoided. When the method accord¬ ing to the present invention is applied, the tin layers deposited exhibit an excel¬ lent quality with respect to the joinability and the durability and the useful life of the tin bath can be extended such that an economic application becomes pos¬ sible.
The subject of the present invention is a method for the currentless metallization of substrate materials containing antimony compounds with tin or tin alloys, comprising the etching, the metallization with a tin salt solution and rinsing the substrate material, characterized in that the method further comprises a pre¬ treatment step wherein the substrate material is contacted with a pretreatment solution prior to the metallization, the pretreatment solution comprising a solu¬ tion of a strong acid, being free of oxidizing agents and removing the antimony compounds from the surface of the substrate material prior to the metallization. Strong acids such mineral acids (sulfuric acid, nitric acid, hydrochloric acid) or strong organic acids such as alkane sulfonic acids can be used as pretreatment solutions.
As it is known to the person skilled in the art, the strength of an acid in an aque- ous solution results from the equilibrium constant Ks(=Ka) of the reaction HX+H2θ=^=^ H3O++X'wherein X" represents the anion of the acid.
The term "strong acids" refers to such acids having an acidity constant Ks of 55.34 to 3.16 • 10"5 corresponding to a pKs of -1.74 to 4.5. Acids having a pKs in the indicated range are used according to the present invention.
The concentration of the sulfuric acid in the pretreatment solution used accord¬ ing to the present invention is 5-60% (parts by weight of the acid / parts by weight of the solution), preferably 10-30%; the concentration of nitric acid is 5-40%, preferably, 5-25%. For example, methane sulfonic acid in a concentra¬ tion of 5-70%, preferably 10-40% can be used as an alkane sulfonic acid. The salts of the acid such as the sodium salt or the potassium salt of methane sulfo¬ nic acid can also be used instead of the acids. In the context of the present in¬ vention, the term "acid solution" designates an aqueous solution of the acid or its salts. Therefore, also a sodium methanesulfonate solution or a potassium methanesulfonate solution is an acid solution for use in the method according to the present invention.
In a particularly preferred embodiment of the method according to the present invention, the substrates to be coated are treated with a hydrochloric acid pre¬ treatment solution. The content of hydrochloric acid is 5-38%, preferably 10- 30%, particularly preferred 15-25% HCI.
The method according to the present invention is usually carried out at a tem¬ perature within the range of 15-8O0C, preferably 30-700C, and most preferably 50-650C. Depending on the pretreatment solution used, particularly on the con¬ centration of the pretreatment solution used, the treatment period is generally within the range of 1-60 minutes, preferably 1-25 minutes, and particularly pre- ferred 2-10 minutes. In the method according to the present invention the antimony compounds dis¬ solved in the pretreatment solution can deposit on the copper surface of the printed circuit boards in the form of antimony. These deposited metal layers can optionally be removed again by a microetching solution.
Such microetching solutions as those usually used to clean copper prior to be¬ ing coated with tin or other final layers are known in the art and practically often consist of an aqueous solution of alkali metal peroxodisulfates or hydrogen per¬ oxide in combination with sulfuric acid. An etching solution for the surface treatment of copper is described in US 6,036,758, the etching solution contain- ing hydrogen peroxide and an aromatic sulfonic acid or its salt. Additionally, this etching solution contains inter alia an inorganic acid, particularly preferred sulfu¬ ric acid. An etching (polishing) solution is known from EP 1 167482, which con¬ tains an N-heterocyclic compound, hydrogen peroxide and a salt of dodecyl benzene sulfonic acid.
Such microetching solutions can further be solutions containing sulfuric acid and peroxodisulfate or its salts or caroates.
The printed circuit board pretreated according to the method of the present in¬ vention can subsequently be metallized chemically in a tin bath. Thereby, the strong dark turbidity of the bath which can otherwise be observed and the for- mation of stains do not occur. The tin final layer exhibits the desired properties such as an excellent joinability and durability.
When the pretreatment of a substrate material containing antimony is carried out on a commercial scale, the pretreatment solution according to the present invention has to be replaced continuously because the concentration of anti- mony dissolved therein increases and, consequently, the antimony deposits on the tin copper layers to be coated with tin. This negatively affects the surface properties of the consecutive tin final layer with respect to durability and joinabil¬ ity. In fact, the antimony can be removed again from the copper by extended etching periods in the microetching step. However, in case of high concentra- tions of antimony in the pretreatment solution the time required for the etching step becomes too long, affecting the cost-effectiveness of the method.
Therefore, it is suggested in an embodiment of the present invention to remove antimony from the pretreatment solution by depositing the antimony on an addi- tional metal.
For this purpose, the pretreatment solution containing antimony compounds is continuously or discontinuously passed over a column containing a metal on which the dissolved antimony species deposits from the pretreatment solution in the form of antimony. The metal can also be added directly to the pretreatment solution. Examples for such metals comprise copper, iron, nickel, cobalt, tin and zinc. The metal can be in the form of granules, rods, bars or spheres, on the surface of which the dissolved antimony deposits.
When the capacity of the column is exhausted due to the surface being com¬ pletely covered with antimony, the column can be regenerated after thorough rinsing by introducing a microetching solution as already described above. After that the column is again available for regenerating the pretreatment solution. The service life of the pretreatment solution can be extended significantly by this measure.
Minor residues of antimony which still deposit on the substrate material and which are dissolved in the tin bath during the metallization can be removed from the tin bath by an additional measure.
For this purpose, the tin bath is continuously or discontinuously passed over metallic tin or metallic tin is directly added to the tin bath. Thereby, antimony contained in the tin bath deposits on the metallic tin and is thus removed from the bath cycle.
To avoid the tin ions concentrating in the tin bath, regeneration methods known in the art can be used. Preferably the regeneration unit disclosed in DE 101 32 478 is used to achieve a constant concentration of tin ions in the solution.
The measures described enable an effective chemical metallization of substrate materials containing antimony such as CEM-1 with tin. The service life of baths for depositing tin and tin alloys is strongly increased and the quality of the re¬ sulting layers is positively influenced with respect to durability and joinability. The pretreatment solution used in the method according to the present inven¬ tion can be regenerated in a further process step. Thereby, the waste water problem is solved to a large extent and the method additionally gains profitabil- ity. Antimony residues which are still leached out of the substrate material in the tin bath and become dissolved, are removed by the regeneration of the tin bath described above by means of metallic tin.
The present invention is described in more detail by means of the following ex¬ amples.
Example 1 :
A printed circuit board made of CEM-1 material having dimensions of 5 x 5 cm is treated with an aqueous solution containing 18% hydrochloric acid at a tem¬ perature of 500C for five minutes. Then the material is treated with a microetch- ing solution ,,Micro Etch SF", available from Atotech, which essentially contains a sulfuric acid solution of peroxodisulfate, at a temperature of 35°C for one min¬ ute and is subsequently metallized with tin by employing Atotech's method for the chemical deposition of tin, comprising the following two steps:
1. Treatment with Stannadip F, essentially containing an acidic solution of tin(ll) methanesulfonate und thiourea at room temperature for one min- ute;
2. Treatment with Stannatech F, essentially containing an acidic solution of tin(ll) methanesulfonate und thiourea at a temperature of 6O0C for five minutes. After the treatment the printed circuit boards are rinsed with de-mineralized wa¬ ter and dried at a temperature of 600C.
The tin layer deposited exhibits a thickness of about 0.5 μm, an excellent dura¬ bility and excellent joining properties in terms of solderability.
The procedure described is repeated for a total of five times. Thereby, the baths for chemical metallization of the printed circuit boards maintain their initial prop¬ erties. The described turbidity and the dark precipitations in the tin bath do not occur. The tin layers deposited do not exhibit any dark stains and their surface properties are maintained.
Example 2:
A printed circuit board made of CEM-1 material having dimensions of 5 x 5 cm is treated with an aqueous solution containing 10% hydrochloric acid at a tem¬ perature of 600C for five minutes. Then the material is treated with a microetch- ing solution ,,Micro Etch SF", available from Atotech, at a temperature of 35°C for one minute and is subsequently metallized with tin by using Atotech's method for the chemical deposition of tin, comprising the following two steps:
1. Treatment with Stannadip F at room temperature for one minute;
2. Treatment with Stannatech F at a temperature of 600C for five minutes.
After the treatment the printed circuit boards are rinsed with VE-water and dried at a temperature of 600C.
The tin layer deposited exhibits a thickness of about 0.5 μm, an excellent dura¬ bility and excellent joining properties in terms of solderability.
The procedure described is repeated for a total of five times. Thereby, the baths for chemical metallization of the printed circuit boards maintain their initial prop- erties. The described turbidity and the dark precipitations in the tin bath do not occur. The tin layers deposited do not exhibit any dark stains and their surface properties are maintained.
Example 3:
The aqueous solution containing 18 % hydrochloric acid for the pretreatment of the printed circuit boards is used in accordance with Example 1. A portion of the solution is continuously removed from the bath and passed over a column filled with copper granules. Thereby, antimony deposits at the surface of the gran¬ ules. When the copper surface is covered with metallic antimony to a large ex¬ tent, the antimony is dissolved by treating with Atotech's microetching solution ,,Micro Etch SF", the solution is removed from the column and supplied to the waste water treatment. The use of this method enabled the treatment of more than 50 printed circuit boards with the hydrochloric acid solution without the ne¬ cessity of replacing the solution.
The pretreated printed circuit boards are processed in accordance with Exam- pie 1 or 2.
Example 4:
A portion of the Stannatech F-solution for metallizing the substrate with tin ac¬ cording to Example 1 is continuously removed from the bath and passed over a column filled with tin granules. Thereby, antimony deposits on the surface of the granules. When the tin surface is covered with metallic antimony to a large ex¬ tent, the antimony is dissolved by treating with Atotech's microetching solution ,,Micro Etch SF", the solution is removed from the column and supplied to the waste water treatment.
The undesired deposition of antimony on the printed circuit boards is prevented by the treatment virtually completely. Example 5:
The Stannatech F-solution for metallizing the substrate with tin in accordance with Example 1 is added with 50 g tin granules. Thereby, antimony deposits on the surface of the granules. When the tin surface is covered with metallic anti- mony to a large extent, the tin granules are removed from the metallizing solu¬ tion and the antimony is dissolved by treating the covered granules with Atotech's microetching solution ,,Micro Etch SF", the solution is supplied to the waste water treatment and the tin granules set free from antimony are supplied back into the metallization solution.
The undesired deposition of antimony on the printed circuit board is prevented virtually completely by the treatment.
Comparative Examples
Comparative Example 1 :
A printed circuit board made of CEM-1 material having dimensions of 5 x 5 cm is treated with Atotech's cleaning agent Pro Select SF which is employed as a standard agent in the conventional metallization of printed circuit boards, at a temperature of 400C for five minutes. Then the material is treated with Atotech's microetching solution ,,Micro Etch SF" at a temperature of 35°C for one minute and is subsequently metallized with tin. For this purpose, Atotech's method for the chemical deposition of tin is employed, the method comprising the following two steps:
1. Treatment with Stannadip F at room temperature for one minute;
2. Treatment with Stannatech F at a temperature at 600C for five minutes. After the treatment the printed circuit boards are rinsed with VE-water and dried at a temperature of 600C.
The tin layer deposited initially exhibits an at least sufficient joinability at a thick¬ ness of about 0.5 μm.
The Stannatech bath loses its initial properties already in the next metallization step. A turbidity and the formation of dark precipitations occur in the tin bath. The tin layer deposited exhibits dark stains and loses its desired surface proper¬ ties. The properties of the tin bath deteriorate rapidly in the following. Already after the fourth step the metallization is incomplete and the bath cannot be used any more.
Comparative Example 2:
A printed circuit board made of CEM-1 material having the size of 5 x 5 cm is treated without pretreatment with Atotech's microetching solution ,,Micro Etch SF" at a temperature of 35°C for one minute and is subsequently metallized with tin. For this purpose, Atotech's method for the chemical deposition of tin is employed, the method comprising the following two steps:
1. Treatment with Stannadip F at room temperature for one minute;
2. Treatment with Stannatech F at a temperature at 6O0C for five minutes.
After the treatment the printed circuit boards are rinsed with VE-water and dried at a temperature of 600C.
The tin layer deposited initially exhibits an at least sufficient joinability at a thick¬ ness of about 0.5 μm.
However, already in the metallization step the Stannatech bath loses its initial properties. A turbidity and the formation of dark precipitations occur in the tin bath. The tin layer deposited exhibits dark stains and loses its desired surface properties. The properties of the tin bath deteriorate rapidly in the following. Al- ready after few method steps the metallization is incomplete. The bath has to be discarded.

Claims

Claims
1. Method for the currentless metallization of substrate materials contain- ing antimony compounds with tin or tin alloys, comprising etching, metal¬ lization with a tin salt solution and rinsing the substrate material, charac¬ terized in that the method further comprises a pretreatment step, wherein the substrate material is contacted with a pretreatment solution prior to metallization, the pretreatment solution comprising a strong acid solution, being free of oxidizing agents and removing the antimony com¬ pounds from the surface of the substrate material prior to metallization.
2. Method according to claim 1 , characterized in that a solution of a min¬ eral acid selected from the group comprising a hydrochloric acid solu¬ tion, a sulfuric acid solution and a nitric acid solution, is used as the pre- treatment solution.
3. Method according to claim 2, characterized in that a hydrochloric acid solution having a concentration of 5-38% is used as the pretreatment solution.
4. Method according to claim 3, characterized in that a hydrochloric acid solution having a concentration of 10-30% is used as the pretreatment solution.
5. Method according to claim 4, characterized in that a hydrochloric acid solution having a concentration of 15-25% is used as the pretreatment solution.
6. Method according to any one of claims 1-5, characterized in that the an¬ timony compounds dissolved in the pretreatment solution are removed from the solution by deposition in a chemical exchange reaction against a metal.
7. Method according to claim 6, characterized in that the solution is passed either continuously or discontinuously over a column filled with a metal to deposit the antimony in a chemical exchange reaction.
8. Method according to claim 6, characterized in that a metal is directly added to the pretreatment solution to deposit the antimony in a chemical exchange reaction.
9. Method according to any one of claims 6-8, characterized in that the metal for depositing antimony in a chemical exchange reaction is in the form of granules, rods, bars or spheres.
10. Method according to any one of claims 6-9, characterized in that the metal for depositing antimony in a chemical exchange reaction is se¬ lected from the group comprising copper, iron, nickel, cobalt, tin and zinc.
11. Method according to any one of claims 6-10, characterized in that the antimony layer which has been formed on a metal in a chemical ex- change reaction, is removed again by treatment with a microetching so¬ lution.
12. Method according to any one of claims 1-11 , characterized in that the antimony compounds contained in the solution used for the metallization with tin or tin alloys are removed from the solution by deposition in a chemical exchange reaction against metallic tin.
13. Method according to claim 12, characterized in that the solution is passed either continuously or discontinuously over a column filled with metallic tin to deposit the antimony in a chemical exchange reaction.
14. Method according to claim 12 or 13, characterized in that the antimony layer, which has been formed on the tin by a chemical exchange reac¬ tion, is removed again by treatment with a microetching solution.
15. Method according to any one of claims 1-14, characterized in that the tin or tin alloy coating is effected from a metallization solution containing tin(ll) methanesulfonate as a tin source.
16. Method according to any one of claims 1-14, characterized in that the tin or tin alloy coating is effected from a metallization solution containing thiourea.
17. Use of the method according to any one of claims 1-6 for producing joinable layers of tin or tin alloys.
18. Use of the method according to any one of claims 1-6 in the manufac¬ ture of a substrate for electric circuitry or in the semiconductor technol¬ ogy in vertical and/or horizontal devices.
19. Use of the method according to claim 18, characterized in that the sup¬ ports for electric circuitry are printed circuit boards.
20. Support for electric circuitry, characterized by having tin or tin alloy lay¬ ers obtainable by the method according to any one of claims 1 to 16.
EP05782911A 2004-08-27 2005-08-25 Method for coating substrates containing antimony compounds with tin and tin alloys Not-in-force EP1807549B1 (en)

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EP05782911A EP1807549B1 (en) 2004-08-27 2005-08-25 Method for coating substrates containing antimony compounds with tin and tin alloys
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2933105B1 (en) 2008-06-27 2010-09-03 Essilor Int NON-ELECTROLYTIC DEPOSITION METHOD
EP2476779B1 (en) * 2011-01-13 2013-03-20 Atotech Deutschland GmbH Immersion tin or tin alloy plating bath with improved removal of cupurous ions
CN102548066A (en) * 2012-02-08 2012-07-04 惠州中京电子科技股份有限公司 PCB (Printed Circuit Board) surface treatment technology
CN102544131A (en) * 2012-03-12 2012-07-04 谢振华 Improved electrode structure for solar battery panel

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891871A (en) * 1956-09-21 1959-06-23 Westinghouse Electric Corp Tin immersion plating composition and process for using the same
US3303029A (en) * 1964-01-23 1967-02-07 Shipley Co Tin coating of copper surfaces by replacement plating
ZA708241B (en) * 1970-01-31 1971-09-29 Norddeutsche Affinerie Process of preventing a supersaturation of electrolytic solutions with one or more of the impurities arsenic antimony,bismuth during the electrolytic refining of non-ferrous metals,particularly copper
US3872210A (en) * 1971-08-11 1975-03-18 Daikin Ind Ltd Process for recovering antimony value out of spent catalyst
US4080513A (en) * 1975-11-03 1978-03-21 Metropolitan Circuits Incorporated Of California Molded circuit board substrate
US4175894A (en) * 1978-05-19 1979-11-27 F. Jos. Lamb Company Boring machine
US4500613A (en) * 1984-03-14 1985-02-19 Lockheed Missiles & Space Company, Inc. Electrochemical cell and method
US4715894A (en) * 1985-08-29 1987-12-29 Techno Instruments Investments 1983 Ltd. Use of immersion tin and tin alloys as a bonding medium for multilayer circuits
JPH0813968B2 (en) * 1987-04-30 1996-02-14 日産化学工業株式会社 Antimony trioxide flame retardant and method for producing the same
US4959121A (en) * 1990-01-05 1990-09-25 General Electric Company Method for treating a polyimide surface for subsequent plating thereon
US5104688A (en) * 1990-06-04 1992-04-14 Macdermid, Incorporated Pretreatment composition and process for tin-lead immersion plating
CN1020503C (en) * 1990-09-13 1993-05-05 清华大学 Optical method for surveying three dimensional figure without reference plane
JP2525521B2 (en) * 1991-06-25 1996-08-21 日本リーロナール株式会社 Electroless tin-lead alloy plating bath
DE4314259C2 (en) * 1993-04-30 1997-04-10 Grundig Emv Process for through-contacting printed circuit boards using conductive plastics for direct metallization
US5391402A (en) * 1993-12-03 1995-02-21 Motorola Immersion plating of tin-bismuth solder
JP3116341B2 (en) * 1995-04-26 2000-12-11 新神戸電機株式会社 Glass woven fabric for laminates and laminate substrates, and methods of using laminates
DE19740431C1 (en) * 1997-09-11 1998-11-12 Atotech Deutschland Gmbh Metallising non-conductive substrate regions especially circuit board hole walls
DE19755185B4 (en) * 1997-12-11 2004-04-08 Ami Doduco Gmbh Exchange tin bath
US6036758A (en) * 1998-08-10 2000-03-14 Pmd (U.K.) Limited Surface treatment of copper
US6541080B1 (en) * 1998-12-14 2003-04-01 Enthone Inc. Double-dip Pd/Sn crosslinker
DE19857290C2 (en) * 1998-12-14 2001-02-01 Lpw Chemie Gmbh Process for the direct metallization of the surface of a plastic object
JP2001291962A (en) * 2000-04-04 2001-10-19 Ibiden Co Ltd Multilayered printed wiring board and producing method therefor
DE10132478C1 (en) * 2001-07-03 2003-04-30 Atotech Deutschland Gmbh Process for depositing a metal layer and process for regenerating a solution containing metal ions in a high oxidation state

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006021445A1 *

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JP2008510885A (en) 2008-04-10
JP4616886B2 (en) 2011-01-19
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US20090081370A1 (en) 2009-03-26
MY143782A (en) 2011-07-15
CN101027427A (en) 2007-08-29
EP1630252A1 (en) 2006-03-01
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KR101188435B1 (en) 2012-10-08
EP1807549B1 (en) 2011-01-12

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